EP0376776B1 - Verfahren für die Keratin-Fasern-Färbung mit Hydroxyindol zusammen mit Chinon und neue 1,4-Benzochinone - Google Patents

Verfahren für die Keratin-Fasern-Färbung mit Hydroxyindol zusammen mit Chinon und neue 1,4-Benzochinone Download PDF

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Publication number
EP0376776B1
EP0376776B1 EP89403358A EP89403358A EP0376776B1 EP 0376776 B1 EP0376776 B1 EP 0376776B1 EP 89403358 A EP89403358 A EP 89403358A EP 89403358 A EP89403358 A EP 89403358A EP 0376776 B1 EP0376776 B1 EP 0376776B1
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Prior art keywords
benzoquinone
alkyl
group
hydroxy
methyl
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English (en)
French (fr)
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EP0376776A2 (de
EP0376776A3 (en
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Arnaud De Labbey
Alain Baudry
Daniel Bauer
Pierre Bore
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LOreal SA
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LOreal SA
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A61K8/347—Phenols
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35—Ketones, e.g. benzophenone
    • A61K8/355—Quinones
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4913—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
    • A61K8/492—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid having condensed rings, e.g. indol
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes

Definitions

  • the present invention relates to a new process for dyeing keratin fibers and more particularly human keratin fibers, such as the hair, using at least one hydroxyindole, associated with at least one quinone derivative as well as new 1, 4-benzoquinones.
  • the methods require the use of an inorganic oxidant constituted in particular by hydrogen peroxide.
  • EP-A-271186 also describes hair dyeing using hydroxyindole derivatives and oxidants, such as periodic acid and periodates, potassium permanganate, sodium hypochlorite, ferricyanide. potassium, potassium dichromate, ammonium persulfate, silver oxide, ferric chloride, lead oxide, calcium sulfate, Fenton's reagent.
  • hydroxyindole derivatives and oxidants such as periodic acid and periodates, potassium permanganate, sodium hypochlorite, ferricyanide.
  • the Applicant has discovered, which is the subject of the invention, that it was possible, surprisingly, to carry out a dyeing using hydroxylated derivatives of indole, without using hydrogen peroxide , ammonia, a metal cation, or a mineral anion, by impregnating the keratin fibers and in particular the hair with the hydroxylated derivative of indole, this impregnation being preceded or followed by the application of a composition containing a derivative quinonic.
  • the Applicant has discovered, in particular, that it is particularly easy to dye natural hair in a wide variety of tones, from light shades to dark shades.
  • the subject of the invention is therefore a new process for dyeing keratin fibers and in particular human keratin fibers, using a hydroxylated derivative of indole and, as oxidizing agent, a quinone derivative.
  • composition (A) is applied to these fibers, containing, in a medium suitable for dyeing, at least one mono or dihydroxyindole, the application of composition (A) being preceded or followed by the application of a composition (B) containing, in a medium suitable for dyeing, at least a quinone derivative chosen from ortho-or parabenzoquinones, ortho- or parabenzoquinones monoimines or diimines, ortho- or parabenzoquinones sulfonimides, a, ro-alkylene bis-1,4-benzoquinones, 1,2- or 1,4 -naphthoquinones, 1,2- or 1,4-naphthoquinone-monoimines or diimines; the mono- or dihydroxyindoles and the quinone derivatives being chosen so that the difference in redox potential AE between the
  • the alkyl radicals, linear or branched C 1 -C 20 are particularly chosen from methyl, ethyl, propyl, butyl, hexadecyl;
  • the aralkyl group is preferably a benzyl group;
  • the C 2 -C 20 acyl group is preferably chosen from acetyl, propionyl, butanoyl, pivaloyl, hexanoyl, myristoyl, hexadecanoyl groups;
  • the C 3 -C 20 alkenoyl group, linear or branched is preferably chosen from butenoyl and oleyl radicals.
  • halogen is preferably chosen from fluorine, chlorine or bromine.
  • a subject of the invention is also new 1,4-benzoquinones of formula: wherein A represents the groupings -CH 2 SR or SR, wherein R denotes an alkyl group C 1 -C 4 hydroxyalkyl or C 1 -C 4 alkyl; R 21 represents a hydrogen atom, a C 1 -C 4 alkyl radical or the group SR, Radiating the meaning mentioned above, provided that R 21 represents a hydrogen atom when A denotes the group -CH 2 SR,
  • R ' 1 , R' 2 , R ' 3 , R' 4 , R 16 , R 17 , R 18 denote hydrogen, C l -C 4 alkyl, C 1 - alkoxy - C 4 , halogen, acyl (C 2 -C 6 ) amino or S0 3 H.
  • the particularly preferred combinations are chosen from the combination of 5,6-dihydroxyindole with 1,4-benzoquinone, 2-methyl 1,4-benzoquinone, 2,6-dimethyl 1,4 -benzoquinone, 2-methoxy 1,4-benzoquinone, 2-chloro 1,4-benzoquinone, 2,3,5-trichloro 6-methyl 1,4-benzoquinone, 2-acetylamino 1,4-benzoquinone, 2-acetylamino 3-methoxy 1,4-benzoquinone, 2,6-dimethyl 5-acetylamino 1,4-benzoquinone, 2,3-dimethoxy 1,4-benzoquinone, 2-methoxymethyl 1,4-benzoquinone, 2- ⁇ -hydroxyethyl 1,4-benzoquinone, 2- ⁇ , y-dihydroxypropylthio 1,4-benzoquinone, 2- ⁇ -carboxyethylthio 1,4-benzo
  • the concentration of mono- or the dihydroxyindole used in composition (A) is preferably between 0.01 and 0.3 mole / liter.
  • compositions (A) and (B) can be packaged in the forms usually used, in particular in hair dyeing, in particular in the form of a more or less thickened lotion, gel, emulsion optionally packaged in aerosol form.
  • the medium suitable for dyeing is generally an aqueous medium which may consist of water or a mixture of water and a solvent which, when the composition is applied to the hair, must be cosmetically acceptable.
  • Such solvents are chosen more particularly from organic solvents, such as lower Ci-Ce alcohols such as ethyl alcohol, propyl or isopropyl alcohol, tert-butyl alcohol, ethylene glycol, propylene glycol, ethers nonomethyl, monoethyl or monobutyl of ethylene glycol, monoethyl ether of ethylene glycol acetate, monomethyl ethers of propylene glycol and dipropylene glycol, methyl lactate.
  • organic solvents such as lower Ci-Ce alcohols such as ethyl alcohol, propyl or isopropyl alcohol, tert-butyl alcohol, ethylene glycol, propylene glycol, ethers nonomethyl, monoethyl or monobutyl of ethylene glycol, monoethyl ether of ethylene glycol acetate, monomethyl ethers of propylene glycol and dipropylene glycol, methyl lactate.
  • Particularly preferred solvents are ethyl alcohol and propylene glycol.
  • the solvents when used, are more particularly in concentrations of between 10 and 50% for lower alcohols and for high concentrations of mono- or dihydroxyindole.
  • compositions (A) and (B) in accordance with the invention can also be stored in an anhydrous solvent medium.
  • the solvents are chosen from the solvents defined above.
  • An anhydrous medium is a medium containing less than 1% water.
  • compositions in accordance with the invention when they are used for dyeing the hair, may also contain any other adjuvants usually used in cosmetics and more particularly anionic, cationic, non-ionic, amphoteric surfactants or their mixtures, thickening agents, perfumes, sequestering agents, film-forming agents, treatment agents, dispersing agents, conditioning agents, preserving agents, opacifying agents, keratin fiber swelling agents.
  • adjuvants usually used in cosmetics and more particularly anionic, cationic, non-ionic, amphoteric surfactants or their mixtures, thickening agents, perfumes, sequestering agents, film-forming agents, treatment agents, dispersing agents, conditioning agents, preserving agents, opacifying agents, keratin fiber swelling agents.
  • compositions (A) and / or (B) which can be used in the process according to the invention may contain other dyes usually used for dyeing keratin fibers and in particular direct dyes, such as benzene nitrates, oxidation dyes of the para or ortho type and so-called "fast" couplers or oxidation dyes, that is to say molecules with a benzene structure, dye precursors capable of generating the colored compounds by simple oxidation with l air during the exposure time on the hair which is generally less than 1 hour and in the absence of any other oxidizing agent.
  • direct dyes such as benzene nitrates, oxidation dyes of the para or ortho type and so-called "fast" couplers or oxidation dyes, that is to say molecules with a benzene structure
  • dye precursors capable of generating the colored compounds by simple oxidation with l air during the exposure time on the hair which is generally less than 1 hour and in the absence of any other oxidizing agent.
  • compositions may also contain quinone dyes from the family of benzoquinones, benzoquinones imines or diimines, naphthoquinones, naphtoquinone-imines or naphtoquinonediimines, which do not meet the potential conditions defined above. These dyes are, in this case, used to bring their own shade to the dye.
  • the different compositions can be packaged in a device with several compartments also called a "kit” or dye kit comprising all the components intended to be applied for the same dye on the keratin fibers and in particular the hair, in successive applications with or without premix.
  • kit or dye kit comprising all the components intended to be applied for the same dye on the keratin fibers and in particular the hair, in successive applications with or without premix.
  • Such devices may more particularly comprise a first compartment containing the composition (A) and a second compartment comprising the composition (B).
  • Another variant may also consist in storing the composition (A) or the composition (B) in an anhydrous solvent medium and in providing a third compartment containing an aqueous medium suitable for dyeing and cosmetically acceptable if the compositions are intended to be applied to the hair.
  • the contents of the third compartment are mixed just before use in one or the other or the two compartments containing the anhydrous compositions (A) and (B).
  • the process in accordance with the invention is preferably carried out by first applying the composition (A) and secondly, the composition (B). It can be used, in particular, to dye human hair, natural or already dyed, permed or not, or straightened, hair strongly or slightly discolored and possibly permed.
  • the composition (A) is applied at a temperature which can be supported by the head, that is to say between 25 and 40 ° C., for 2 to 30 minutes and followed with or without rinsing.
  • the dyeing temperature is also between 25 and 40 ° C.
  • the process according to the invention can also be implemented, with a view to nuancing or refreshing a dye which would have been carried out using mono- or dihydroxyindole, by applying composition (B) several hours or days after dyeing using mono- or dihydroxyindoles.
  • the compound of formula (VII) is obtained by reduction of the compound of formula (VIII) where R has the meanings defined above.
  • R has the meanings defined above.
  • conventional reduction methods mention may be made of reduction by sodium hydrosulfite in an alkaline medium at a temperature below 80 ° C., or else a catalytic reduction in a hydroalcoholic medium, under hydrogen pressure, in the presence of a catalyst such as Palladium on carbon or Nickel.
  • the compound of formula (VIII) can be prepared by the action of a thiolate of formula: in which M represents an alkali or alkaline earth metal and R has the meanings defined above on the compound of formula (IX).
  • the thiolate can advantageously be prepared in situ according to the reaction scheme: the HSR compound can also serve as a solvent.
  • the reaction temperature is less than 100 ° C.
  • These compounds IV (B) are prepared from the benzoquinonic compounds of formula (X) by reacting, in an alcohol / water solvent or in ethanol, two moles of the quinone derivative with one mole of thiol (RSH) according to the reaction scheme. II.
  • a lock of 1 g of natural hair containing 90% white hairs is impregnated with 5 ml of a 2.5% 5.6-dihydroxyindole solution in 90/10 hydroethanol medium for 15 minutes. Rinse the wick under running water and wring it out. This wick is again impregnated with 5 ml of a 2% solution of 1,4-benzoquinone in a 50/50 hydroethanolic medium for 8 minutes. The wick is rinsed under running water and shampooed with an aqueous solution of sodium lauryl sulfate at 5%. We obtain a wick whose color is intense black with slight bluish reflections.
  • a lock of 1 g of gray natural hair (90% white) is impregnated with 5 ml of a 2.5% solution of 4-hydroxy 5-methoxy indole in 50/50 hydroethanolic solution. for 15 minutes at room temperature. Rinse the wick under running water and wring it out. This same wick is impregnated, in a second step, with 5 ml of a 2% solution of 1,4-benzoquinone in 50/50 hydroethanolic medium, for 8 minutes. Wash with running water and finish with a 5% sodium lauryl sulfate shampoo. An intensely colored wick is obtained, the shade of which is purple.
  • a lock of 1 g of gray natural hair (90% white) is taken and impregnated for 15 minutes with a 60/40 hydroethanol solution of 2-methyl 5,6-dihydroxyindole at 2.5%.
  • the wick is washed with running water and then wrung out.
  • 5 ml of a 2% solution of 1,4-benzoquinone are again applied in a 50/50 hydroalcoholic medium for 9 minutes.
  • the lock is washed with running water and then shampooed with 5% sodium lauryl sulfate. We obtain a wick whose color is black-raven.
  • a 2.5% solution of 6-hydroxy 7-methoxy indole is prepared in an 80/20 hydroalcoholic medium. 5 ml of this solution are applied to a lock of 1 g of natural hair (gray with 90% white), for 15 minutes. Rinse the wick under running water, then wring it out. This wick is again impregnated for 10 minutes with 5 ml of a 50/50 hydroalcoholic solution of 2% 1,4-benzoquinone. The wick is rinsed with water and ended with a 5% sodium lauryl sulfate shampoo. We obtain a lock of brown color.
  • a 2.5% solution of 5-methoxy 6-hydroxyindole is prepared in a 70/30 hydroalcoholic solution. This solution is left to stand on a lock of gray hair containing 90% white hair for 15 minutes, at room temperature. It is rinsed, wrung, then the color is revealed with a 50/50 hydroalcoholic solution at 2% of 1,4-benzoquinone. The exposure time is 8 minutes and after rinsing, shampooing, rinsing and drying, a black color is obtained.
  • a lock of natural gray hair, 90% white hair, is pretreated for 15 minutes with a 60/40 hydroalcoholic solution containing 2.5% of 5-hydroxy 6-methoxyindole.
  • the exposure time is 15 minutes and after rinsing and spinning, it is revealed by a hydroalcoholic solution 50/50, 2% of 1,4-benzoquinone.
  • the exposure time is 8 minutes and after rinsing, shampooing, rinsing again and drying, a light chestnut color is obtained.
  • An 80/20 hydroalcoholic solution of 2.5% 7-hydroxyindole is applied to a lock of natural gray hair containing 90% white hair. Leave to stand for 15 minutes, rinse, wring and apply a 50/50 hydroalcoholic solution containing 2% of 1,4-benzoquinone. Leave on for 15 minutes, wash, wring, dry and a very intense dark purple color is obtained.
  • a lock of gray hair is treated with an 80/20 hydroalcoholic solution containing 2.5% of 6-hydroxyindole. After an exposure time of 15 minutes, the wick is rinsed, wrung and applied a composition based on water / alcohol 50/50 and 2% 1,4-benzoquinone. Leave to stand for 9 minutes, after which, wash with shampoo, rinse, dry and obtain a golden brown color.
  • a lock of naturally gray hair containing 90% white hair is treated with a 60/40 hydroalcoholic solution of 1% of (5 or 6) -acetoxy (6 or 5) -hydroxyindole. It is left to stand for 15 minutes, after which it is rinsed, wrung and applied a 50/50 hydroalcoholic solution of 2% of 1,4-benzoquinone. Leave to sit for 8 minutes, then wash, rinse, wring and obtain a golden brown color.
  • a lock of naturally gray hair is treated with an 80/20 hydroalcoholic solution containing 2.5% of 5,6-dihydroxyindole. After an exposure time of 15 minutes, rinsing and spinning, the color is revealed by 2-methyl 1,4-benzoquinone (toluquinone) dissolved at 2% in a 50/50 hydroalcoholic solution. After rinsing, washing, rinsing again and drying, we obtain an intense black color with bluish reflections.
  • 2-methyl 1,4-benzoquinone toluquinone
  • a lock of natural gray hair containing 90% white hairs is treated with a 50/50 hydroethanolic solution containing 2.5% of 5,6-dihydroxyindole. After 15 minutes of exposure time, the wick is rinsed, wrung and applied a 50/50 hydroethanol composition containing 2% of 1,2-tetrachloro-benzoquinone. Leave to stand for 10 minutes, rinse, wash with shampoo, rinse again and dry. We get a dark curd color.
  • the pretreatment composition is the same as in Example 16 and that of disclosure is based on 2,6-dimethyl 5-acetylamino 1,4-benzoquinone. A light gray chestnut color is obtained.
  • the pretreatment is the same as in Example 16. It is followed by a revelation with a 50/50 hydroalcoholic solution at 2% of 1,4-naphthoquinone. Leave on for 8 minutes, rinse, wash, rinse again and dry. We observe a light chestnut color.
  • Example 16 The procedure is as in Example 16, the development being carried out using N-2,6-trichloro 1,4-benzoquinone-imine. The color obtained is dark chestnut.
  • Composition (A) is identical to that of Example 23.
  • Composition (A) is identical to that of Example 23.
  • composition and the mode of pretreatment are the same as in Example 16. They are followed by a revelation with a 50/50 hydroalcoholic solution at 2% of 2-chloro 1,4-benzoquinone for 10 minutes. We rinse, wash and dry the hair.
  • the color obtained is intense black.
  • a lock of gray hair containing 90% white hairs is treated with a 90/10 hydroalcoholic solution of 2.5% of 2,3-dimethyl 5-hydroxy 6-amino indole. It is left in contact for 15 minutes, rinsed, wrung and applied a 50/50 hydroalcoholic solution containing 2% of 1,2-naphthoquinone. The contact time is 15 minutes, washing, wringing, drying and a dark gray color is obtained.
  • a lock of gray hair containing 90% white hairs is treated with a 90/10 hydroalcoholic solution of 2.5% of 2,3-dimethyl 5-amino 6-hydroxy indole. It is left in contact for 15 minutes, rinsed, wrung and applied a 50/50 hydroalcoholic solution containing 2% of 1,4-benzoquinone. The contact time is 15 minutes, washing, wringing, drying and obtaining a medium brown color.

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Claims (23)

1. Verfahren zum Färben von Keratinfasern, dadurch gekennzeichnet, daß man auf die Fasern wenigstens ein Mittel A aufträgt, welches in einem zum Färben geeigneten Medium wenigstens ein Mono- oder Dihydroxyindol enthält, wobei man das Mittel A vor oder nach Auftragen eines Mittels B anwendet, welches in einem zum Färben geeigneten Medium wenigstens ein Chinonderivat enthält, das ausgewählt ist unter o- und p-Benzochinonen, o- und p-Benzochinonmonoiminen oder-diiminen, 1,2- oder 1,4-Naphthochinonen, o- oder p-Benzochinonsulfonimiden, α,ω-Alkylen-bis-1,4-benzochinonenoder 1,2- oder 1,4-Naphtochinonmonoiminen oder -diiminen, wobei die Mono- oder Dihydroxyindole und die Chinonderivate so ausgewählt werden, daß die Redoxpotentialdifferenz ΔE zwischen dem bei pH 7 in einem Phosphatmilieu mit einer Glaskohlenstoffelektrode durch Voltametrie bestimmten Redoxpotential E der Mono- oder Dihydroxyindole und dem bei pH 7 in einem Phosphatmilieu durch Polarographie mit einer Quecksilberelektrode gegen eine gesättigte Kalomelelektrode bestimmten Redoxpotential Eq der Chinonderivate folgender Bedingung genügt:
Figure imgb0122
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Mono- oder Dihydroxyindole ausgewählt sind unter Verbindungen der Formel:
Figure imgb0123
worin R1 ein Wasserstoffatom oder eine C1-C4-Alkylgruppe bedeutet;
R2 und R3, die gleich oder verschieden sein können, ein Wasserstoffatom, eine C1-C4-Alkylgruppe, Carboxylgruppe, C1-C4-Alkoxycarbonylgruppe, Hydroxy-C1-C4-alkylgruppe oder Amino-C1-C4-alkylgruppe bedeuten;
R4, R5, R6 und R7 unabhängig voneinander für ein Wasserstoffatom, C1-C4-Alkyl, eine gegebenenfalls durch eine oder zwei C1-C4-Alkyl- oder-Hydroxyalkylgruppen substituierte Aminogruppe, C2-C6-Acylamino, Carboxyl, Carboxy-C1-C4-alkyl, C1-C4-Alkoxycarbonyl,
Figure imgb0124
 (worin rund r' unabhängig voneinander für ein Wasserstoffatom oder eine C1-C4-Alkylgruppe stehen), Halogen, C1-C4-Hydroxyalkyl, C1-C4-Aminoalkyl, OH oder OZ steht, wobei Z für eine geradkettige oder verzweigte C1-C20-Alkylgruppe Aralkylgruppe, Formylgruppe, geradkettige oder verzweigte C2-C20-Acylgruppe, geradkettige oder verzweigte C3-C20-Alkenylgruppe, für -SiR11R12R13, -P(O)(OR8)2 oder R8OSO2- steht, wobei die Reste R4 und R5 oder R5 und R6 oder R6 und R7 zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, einen Ring bilden können, der gegebenenfalls eine Carbonylgruppe, eine Thiocarbonylgruppe, die Gruppen P(O)(OR8) oder CR9R10 enthält, unter der Bedingung, daß wenigstens einer der Reste R4 bis R7 für OH steht;
R8 und Rg ein Wasserstoffatom oder eine C1-C4-Alkylgruppe bedeuten;
R10 eine C1-C4-Alkoxygruppe oder eine Mono- oder Di-C1-C4-alkylaminogruppe bedeutet;
R11' R12 und R13, die gleich oder verschieden sein können, eine gradkettige oder verzweigte C1-C4-Alkylgruppe bedeuten und
den entsprechenden Alkalimetall-, Erdalkalimetall-, Ammonium- und Aminsalzen dieser Verbindungen.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Mono- oder Dihydroxyindole ausgewählt sind unter:
4-Hydroxyindol,
4-Hydroxy-5-methoxyindol,
4-Hydroxy-5-ethoxyindol,
5-Hydroxyindol,
2-Carboxy-5-hydroxyindol,
5-Hydroxy-6-methoxyindol,
6-Hydroxyindol,
6-Hydroxy-7-methoxyindol,
5-Methoxy-6-hydroxyindol,
2-Carboxy-6-hydroxyindol,
2-Ethoxycarbonyl-6-hydroxyindol,
7-Hydroxyindol,
2,3-Dimethyl-7-hydroxy-4-methoxyindol,
5,6-Dihydroxyindol,
1-Methyl-5,6-dihydroxyindol,
2-Methyl-5,6-dihydroxyindol,
3-Methyl-5,6-dihydroxyindol,
2,3-Dimethyl-5,6-dihydroxyindol,
(5 oder 6)-Acetoxy-(6 oder 5)-hydroxyindol,
2-Ethoxycarbonyl-5,6-dihydroxyindol,
2-Carboxy-5,6-dihydroxyindol,
2,3-Dimethyl-5-hydroxy-6-aminoindol,
2,3-Dimethyl-5-amino-6-hydroxyindol.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Chinonderivate ausgewählt sind unter Verbindungen der Formeln (ll) und (ll'):
Figure imgb0125
worin X für ein Sauerstoffatom oder die Gruppe NR19 steht; Y für ein Sauerstoffatom oder die Gruppe NR20 steht;
R19 und R20, die gleich oder verschieden sein können, ein Wasserstoff- oder Halogenatom, eine Alkylgruppe, C1-C4-Hydroxyalkylgruppe, C1-C4-Alkylsulfonylgruppe oder Phenylsulfonylgruppe stehen;
R14, R15, R16, R17 und R18 unabhängig voneinander für ein Wasserstoffatom, C1-C4-Alkyl, Carboxyl, C1-C4-Alkylcarbonyl, C1-C4-Alkoxycarbonyl, C1-C4-Alkoxymethyl, C1-C4-Alkylthiomethyl, Hydroxy-C1-C4- alkylthiomethyl, Hydroxy-C1-C4-alkylsulfinyl,
Figure imgb0126
(worin rund r' unabhängig voneinander für ein Wasserstoffatom oder eine C1-C4-Alkylgruppe stehen), Carboxyalkyl, Halogen, C1-C4-Hydroxyalkyl, eine gegebenenfalls durch eine oder zwei C1-C4-Alkyl- oder -Hydroxyalkylgruppen substituierte Aminogruppe, C2-C6-Acylamino, SO3M, wobei M ein Wasserstoffatom, K oder Na bedeutet, eine Sulfoxid-, Sulfon- oder gegebenenfalls substituierte Sulfonamidgruppe, für OZ1, worin Z1 ein Wasserstoffatom, C1-C4-Alkyl, Hydroxy-C1-C4-alkyl, Carboxy-C1-C4-alkyl, gegebenenfalls durch C1-C4-Alkoxy substituiertes Phenyl bedeutet, oder für -SZ2 steht, worin Z2 für C1-C4-Alkyl, C1-C4-Hydroxyalkyl, C2-C4-Dihydroxyalkyl oder Carboxy-C1-C4-alkyl steht;
R14 und R15 zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, den folgenden Ring bilden können:
Figure imgb0127
worin R'1, R'2, R'3 und R'4 die oben für R14, R15, R16, R17 und R18 angegebenen Bedeutungen besitzen, wenn diese keinen Ring bilden.
i. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Chinonderivate ausgewählt sind unter Benzochinonen der Formeln:
Figure imgb0128
worin R14, R15, R16, R17 und R18 unabhängig voneinander für ein Wasserstoffatom, C1-C4-Niedrigalkyl, C1-C4-Niedrigalkoxy, Halogen, C2-C6-Acylamino, SO3M, C1-C4-Alkoxymethyl, Carboxy-C1-C4-alkyl, C1-C4-Alkoxycarbonyl, Dialkylamino, OZ1, worin Z1 Carboxy-C1-C4-alkyl, C1-C4-Hydroxyalkyl bedeutet, oder SZ2 stehen, worin Z2 für C1-C4-Hydroxyalkyl, C1-C4-Dihydroxyalkyl, Carboxy-C1-C4-Alkyl oder C1-C4-Alkyl steht;
X für ein Sauerstoffatom oder die Gruppe NR19 steht;
Y für ein Sauerstoffatom oder die Gruppe NR20 steht,
R19 und R20 unabhängig voneinander ein Wasserstoff- oder Halogenatom, C1-C4-Niedrigalkyl, Methylsulfonyl oder Phenylsulfonyl bedeuten.
6. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Chinonderivate ausgewählt sind unter Verbindungen der Formeln:
Figure imgb0129
worin R'1, R'2, R'3, R'4, R16, R17 und R18 die in den Ansprüchen 4 und 5 angegebenen Bedeutungen besitzen und
X und Y die in Anspruch 5 angegebenen Bedeutungen besitzen.
7. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Chinonderivate ausgewählt sind unter folgenden Verbindungen:
1,4-Benzochinon, 2-Methoxy-1,4-benzochinon, 2-Methyl- 1,4-benzochinon, 2,6-Dimethyl-1,4-benzochinon, 2,3,5-Trichlor -6-methyl-1,4-benzochinon, 2-Acetylamino-1,4-benzochinon, 2-Acetylamino-3,5-dimethyl-1,4-benzochinon, 2,6-Dimethyl-5-acetylamino-1,4-benzochinon, tetrachlor-1,2-benzochinon, 2-Chlor-1,4-benzochinon, 2,3-Dimethoxy- 1,4-benzochinon, 2-ß-Carboxyethoxy-1,4-benzochinon, 2-Methoxymethyl-1,4-benzochinon, 2-β-Hydroxyethyl-1,4-benzochinon, 2-ß-Hydroxyethylthio-1,4-benzochinon, 2,5-Bis-β-hydroxyethyithio-l ,4-benzochinon, 2-β,γ-Dihydroxypropyithio -1,4-benzochinon, 2-β-Carboxyethylthio-1,4-benzochinon, 2-Carboxymethyl-1,4-benzochinon, 2-ß-Hydroxyethylthio -6-methyl-1,4-benzochinon, 2-Methoxycarbonyl -3-methoxy-1,4-benzochinon, 2-Methoxycarbonyl- 1,4-benzochinon, 2-Methylthio-1,4-benzochinon, 2-Dimethylamino -1,4-benzochinon, 2-Acetylamino-5-methoxy- 1,4-benzochinon, 2-(ß-Hydroxyethylthio)-methyl-1,4-benzochinon, 2-(Methylthio)-methyl-1,4-benzochinon, 4,5-Dimethoxy-1 ,2-benzochinon, 4-Methyl-5-chlor-1,2-benzochinon,4,5-Dimethyl-1 ,2-benzochinon, 2,3-Dimethyl-1,4-benzochinon, 2-β-Hydroxyethoxy-1,4-benzochinon, N-Methylsulfonyl-1,4-benzochinon-mo- noimin, N-Phenyl-sulfonyl -1,4-benzochinon-monoimin, 1,4-Naphthochinon, 1,2-Naphthochinon, 1,2-Naphthochinon-4-sulfonsäure, 2,3-Dichlor-1 ,4-naphthochinon, N,2,6-Trichlor-1,4-benzochinonimin.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß das Mittel A 5,6-Dihydroxyindol enthält und das Mittel B ein Chinonderivat enthält, das ausgewählt ist unter 1,4-Benzochinon, 2-Methyl-1,4-benzochinon 2,6-Dimethyl-1,4-benzochinon, 2-Methoxy- 1,4-benzochinon, 2-Chlor-1,4-benzochinon, 2,3,5-Trichlor -6-methyl-1,4-benzochinon, 2-Acetylamino-1,4-benzochinon, 2-Acetylamino-3-methoxy-1,4-benzochinon, 2,6-Dimethyl -5-acetylamino-1,4-benzochinon, 2,3-Dimethoxy- 1,4-benzochinon, 2-Methoxymethyl-1,4-benzochinon, 2-β-Hydroxyethyl-1,4-benzochinon, 2-β,-γ-Dihydroxypropytthio - 1,4-benzochinon, 2-β-Carboxyethylthio-1,4-benzochinon, 2-Carboxymethyl-1,4-benzochinon, 1,4-Naphthochinon, N-2,6-Trichlor-1,4-benzochinonimin, 1,2-Naphthochinon, 1,2-Naphthochinon-4-sulfonsäure.
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß das Mono- oder Dihydroxyindol im Mittel A in einer Konzentration zwischen 0,01 und 0,3 Mol/l enthalten ist.
10. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß das Chinonderivat im Mittel B in einer Konzentration zwischen 0,005 und 1 Mol/l enthalten ist.
11. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß der pH-Wert der Mittel A und B unabhängig voneinander zwischen 2 und 10 liegt.
12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß der pH-Wert des Mittels B sauer ist.
13. Verfahren nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß die Mittel A und B ein wäßriges Milieu umfassen, das aus Wasser oder einer Mischung von Wasser und einem Lösungsmittel besteht.
14. Verfahren nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß die Mittel A und B in einem wasserfreien Lösungsmittelmilieu vorliegen.
15. Verfahren nach einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, daß die Mittel A und B anionische, kationische, nicht-ionische, amphotere Tenside oder Mischungen davon, Verdickungsmittel, Parfüms, Sequestrier-mittel, filmbildende Mittel, Behandlungsmittel, Dispergiermittel, Konditioniermittel, Konservierungsmittel, opakmachende Mittel oder Mittel zur Quellung von Keratinfasern enthalten.
16. Verfahren nach einem der Ansprüche 1 bis 15, dadurch gekennzeichnet, daß das Mittel A und/oder B weitere Farbstoffe enthält, die ausgewählt sind unter Direktfarbstoffen, Oxidationsfarbstoffen, Kupplern oder "Schnell"-Oxidationsfarbstoffen.
17. Verfahren nach einem der Ansprüche 1 bis 16, dadurch gekennzeichnet, daß das Mittel A und/oder B außerdem Chinonfarbstoffe der Familie der Benzochinone, Benzochinonimine oder-diimine, Naphthochinone, Naphthochinonimine, Naphthochinondiimine oder Indolchinone enthält, deren Potential AE größer als 320 mV ist.
18. Vorrichtung aus mehreren Abteilen oder Färbekit, dadurch gekennzeichnet, daß in einem ersten Abteil das Mittel A wie in einem der Ansprüche 1 bis 17 definiert und in einem zweiten Abteil das Mittel B wie in einem der Ansprüche 1 bis 17 definiert, enthalten ist.
19. Vorrichtung nach Anspruch 18, dadurch gekennzeichnet, daß wenigstens eines der Mittel A und B ein wasserfreies Lösungsmittelmilieu umfaßt und ein drittes Abteil ein wäßriges Milieu zum Färben enthält, das dazu bestimmt ist, unmittelbar vor Gebrauch mit dem Inhalt eines der beiden Abteile vermischt zu werden, welches die wasserfreien Mittel A und B enthält.
20. Neue Verbindungen der Formel:
Figure imgb0130
worin A die Gruppe CH2SR bedeutet, wobei Reine C1-C4-Alkyl- oder C1-C4-Hydroxyalkylgruppe bedeutet; und R21 ein Wasserstoffatom bedeutet.
21. Neue Verbindungen der Formel:
Figure imgb0131
 worin A die Gruppe SR bedeutet, wobei R eine C1-C4-Hydroxyalkylgruppe bedeutet; R21 ein Wasserstoffatom, eine C1-C4-Alkylgruppe oder die Gruppe SR bedeutet, wobei R die oben angegebene Bedeutung besitzt.
22. Verwendung der Verbindungen der Ansprüche 20 oder 21 in Färbemitteln für Keratinfasern.
23. Verfahren zur Herstellung der Verbindungen der Formel (IV), worin A für CH2SR steht und R21 ein Wasserstoffatom bedeutet, dadurch gekennzeichnet, daß man ein p-Aminophenol der Formel:
Figure imgb0132
worin R die im Anspruch 20 angegebenen Bedeutungen besitzt, mit Eisen(lll)-chlorid oder Eisen(lll)-sulfat oxidiert.
EP89403358A 1988-12-06 1989-12-05 Verfahren für die Keratin-Fasern-Färbung mit Hydroxyindol zusammen mit Chinon und neue 1,4-Benzochinone Expired - Lifetime EP0376776B1 (de)

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ZA899322B (en) 1990-09-26
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